New azomethine pigments and processes for their manufacture

ABSTRACT

Azomethine pigments of the formula   WHEREIN THE SUBSTITUENTS X, Y, Z, X1 and Y1 denote H or halogen atoms or alkyl or alkoxy groups containing 1 - 6 C atoms, or wherein the substituents X and Y form a fused benzene ring, and metal complexes of these pigments, are useful for coloring plastics and lacquers in yellow to orange shades of good fastness properties.

United States Patent [191 Frey AZOMETHINE PIGMENTS AND PROCESSES FOR THEIR MANUFACTURE [75] Inventor: Christoph Frey, Oberwil,

Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Aug. 3, 1973 [21] Appl. No.: 385,618

[30] Foreign Application Priority Data Aug. 9, 1972 Switzerland 11763/72 [52] U.S. Cl. 260/270 Q; 260/37 N; 260/37 P;

260/270 K; 260/288 R; 260/289 R; 260/3261; 8/42 A; 8/42 B; 8/42 C; 8/42 D; 8/42 R; 106/288 Q 11] 3,892,750 [4 1 July 1,1975

Primary ExaminerDonald G. Daus Assistant Examiner-Mark L. Berch Attorney, Agent, or FirmVincent l. Cavalieri [57] ABSTRACT Azomethine pigments of the formula wherein the substituents X, Y, Z, X and Y denote H or halogen atoms or alkyl or alkoxy groups containing 1 6 C atoms, or wherein the substituents X and Y form a fused benzene ring, and metal complexes of these pigments, are useful for coloring plastics and lacquers in yellow to orange shades of good fastness properties,

7 Claims, No Drawings It has been found that new valuable azomethines of the formula wherein the substituents, X, Y, Z, X and Y denote H or halogen atoms or alkyl or alkoxy groups containing l-6 C atoms, or wherein the substituents X and Y form a fused benzene ring, as well as metal complexes of these pigments, are obtained when a 2,4- dihydroxyquinoline of the formula is condensed with a naphthostyril of the formula N .H Hal.

wherein R denotes an alkyl group and Hal denotes a halogen atom, and the resulting condensation product is metallised if desired.

Since the dyestuffs according to the invention are pigments, groups which confer solubility in water, especially acid groups which confer solubility in water, such as sulphonic acid groups or carboxylic acid groups, must of course not be present.

Particular interest attaches to azomethine metal complexes of the probable formula wherein M is a divalent metal atom, especially a nickel, copper or cobalt atom and X, Y, Z, X, and Y, have-the indicated meaning.

1 dihydroxyquinoline,

-The following known compounds may be mentioned as examples of 2,4-dihydroxyquinolines: 2,4-

Dihydroxyquinoline, 6-chloro2,4dihydroxyquinoline,

6,7-dichloro-2,4- 7,8-dichloro-2,4- dihydroxyquinoline, 6,7,8-trichloro-2,4- dihydroxyquinoline, 6-methyl-2,4-dihydroxyquinoline. 6-methyl-7-chloro-2,4-dihydroxyquinoline, o-methyl- 8-chloro-2,4-dihydroxyquinoline, and 6,7-dimethyl- 2,4-dihydroxyquinoline.

The known 2-methylmercapto-benzo[c,dJ-indole hydroiodide, and 2-methylmercapt0-6 chloroor -bromobenzo-[c,d]-indole hydroiodide may be mentioned as naphthostyrils.

The, condensation is appropriately carried out in an organic solvent at elevated temperature, preferably between 60 and the boiling point of the solvent used. As examples of solvents there may be mentioned: Alcohol, dioxane, pyridine, dimethylformamide, N- methylpyrrolidone, butyrolactone, glycol monomethyl ether, xylene, chlorobenzene, o-dichlorobenzene or mixtures thereof.

Since the dyestuffs obtained are sparingly soluble in the solvents mentioned, they can easily be isolated by filtration. Any impurities can be removed by elution.

For conversion into the metal complexes, the bisazomethines obtained are treated with agents which donate divalent metals, for example with salts of .zinc, nickel or cadmium, but especially of copperand of cobalt, which give products which are particularly fast to weathering. Preferably, the formates, acetates or stearates of these metals are used. The metallisation is appropriately carried ,out in one of the abovementioned solvents or in a mixture of theabovementioned solvents.

The new dyestuffs are valuable pigments which can be used, in a finely divided form, for pigmenting high molecular organic material, for example cellulose ethers and cellulose esters, such as ethylcellulose,-nitrocellulose, cellulose acetate, cellulose butyrate, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, especially urea-formaldehyde resins and melamineformaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile and polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicones and silicone resins, individually or as mixtures.

It is immaterial whether the high molecular compounds mentioned are in the form of plastic masses or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the end use the new pigments are advantageously used as toners or in the form of preparations.

In the examples which follow the parts, unless otherwise stated, denote parts by weight and the percentages denote percentages by weight.

EXAMPLE 1 16 parts of 2,4-dihydroxyquinoline are added to a solution of 33 parts of 2-methyl-thiobenz-(c,d)-indole hydroiodide of the formula 8-chloro-2,4-dihydroxyquinoline,

C-S-CH in 150 parts of pyridine and the mixture is warmed to 100 105C whilst stirring and kept at this tempera-' ture for 2 hours. After cooling, the precipitate is filtered off, rinsed with methanol and water and dried in vacuo at 8() 100C. An orange-yellow crystal powder of the formula OH N is obtained.

' EXAMPLE N o For the urpose of com lex formation, 4.05 arts of H P P P the product obtained in Example 19, in 100 parts of diis obtained. ethylene glycol monoethyl ether, are heated with 0.97 15 art of nickel acetate to l45l50C whilst stirrin and EXAMPLE 2 p I I w l kept at this temperature for 16 hours. The precipitate.- For the purpose Of complex f I n, P t Of which separates out is filtered off whilst still hot and is the Substance Obtained Example in 100 Parts Of washed with hot o-dichlorobenzene, cold methanol and dimethylformamide, and with the addition of 6.9 parts 7 water, A nge pigment powder is obtained which of cobalt stearate, are heated to 150C for 16 hours, h d d to a fi ly di id d state d ill d in whilst surrmg- The p Pl wh'ch sepflmtes polyvinyl chloride yields an orange sheet which shows filtered Off hot 11nd 1S Washed Wlth hot good fastness to light. A lacquer film pigmented with dichlorobenzene, cold methanol and water. A yellow this pigment has good gtQ light and to weather pigment powder is obtained which when milled in a ing A I i finely d1V1dd f0rm mm Pmyvmyl chlonfje lfmstead of nickel acetate 137 parts of cobalt acetalow Sheet Much gQod f to hght' A q f te.4H- O or copper acetate.H O are used and the procep'gmemed h plgmem'shows good fflsmess dure of the above example is followed, orange pigment to hght and 9 wedthermsf powders which have the same properties are obtained.

If the 2,4-dihydroxyqumolme derivative of column I in the table which follows is condensed according to EXAMPLE Example 1 with 2-methyl-thiobenz-(c,d)-indole hydroiodide and the complex with the metal salt indicated in 65 parts of stabilised polyvinyl chloride, parts of column ll is formed in accordance with Example 2, a dioctyl phthalate and 0.2 part of the dyestuff obtained pigment dyestuff of the Shade sho n in co umn I" iS according to Example 9 are stirred together and then obtained, which when milled into polyvinyl chloride or 35 milled on a two-roll calender for 7 minutes at 1409C. painted out in a lacquer has good fastness to light and A sheet of reddish-tinged yellow colour, having very to weathering. good fastness to light, is obtained.

Table U Example I II III 3 Dihydroxyquinoline 2 Cu stearate V Reddish-tinged yellow 4 Dihydroxyquinoline Ni stearate Yellow 5 fi-Methyl-dihydruxyquinoline Ni stearate Yellow-orange 6 o-Methyl-dihydroxyquinoline Cu acetate Orange 7 6-Methyl-dihydroxyquinoline Co stearatc Yellow-orange 8 o-Chloro-dihydroxyquinoline Ni stearate Yellow-orange 9 fi-Chloro-dihydroxyquinoline Cu acetate Yellow-brown l0 6-Chloro-dihydroxyquinoline C o t stearate Yellow-brown l l 8-Chloro-dihydroxyquinoline Ni stearate Orange l2 8-Chloro-dihydroxyquinoline Co stearate Orange 13 6,7-Dichloro-dihydroxyquinoline Cu acetate Yellow-brown l4 (1.7-Dichloro-dihydroxyquinoline Co acetate Yellow-brown l5 7.8-Dichloro-dihydroxyquinoline Ni acetate Orange 16 7,X-Dichloro-dihydroxyquinoline Cu acetate Reddish-tinged yellow 17 6.7.8-Trichloro-dihydroxyquinoline Ni stearate Yellow-orange l8 6,7,8-Trichloro-dihydroxyquinoline Cu stearate Brownish-tinged yellow I EXAMPLE 22 EXAMPLE l9 r 10 g of titanium dloxide and 2 g of thepigment manu- 18 pa ts Of 6-m hyly r yq m and 44 factured according to Example 2 are'ground with 88 g parts of 2-methylm ercapto-(i-bromo-benzlc,dlof a mixture of 26.4 g of coconut alkyd resin, 24.0 g of mdolehydl'olodlde of the tormula melamine-formaldehyde resin percent solids content), 8.8 gof ethylene 'glycol monomethyl ether and 28.8 g of xylene for 48 hours in aball mill. 3 N-HI I n if this lacquer is sprayed onto an aluminium for], predried for 30 minutes at room temperature and then 3 stoved for 30 minutes at 120C, a yellow lacquering is obtained, which has good colour strength and is distinare warmed to l00lO5C in 250 parts of pyridine and kept at this temperature for 2 hours, whilst stirring. After cooling, the precipitate is filtered off, washed with methanol and water and then dried in vacuo at -l00C. A brown crystal powder of the formula guished by very good fastness to light arid to weathering.

What we claim is: I l 1. An azomethine pigment metal complex of mula' the forwherein M is nickel, copper, cobalt, zinc, or cadmium; and X, Y, Z, X and Y is hydrogen, halogen or alkyl of l to 6 carbon atoms, with the proviso that x, y and z are not simultaneously tertiary alkyl.

2. Metal complex according to claim 1, wherein M denotes a nickel, copper or cobalt atom.

3. The compound of the formula 4. The compound of the formula 5. The compound of the formula 6. The 1:2-cobalt-complex of the dyestuff f the formula 7. The 1:2-cobalt-complex of the dyes 0f the formula 

1. AN AZOMETHINE PIGMENT METAL COMPLEX OF THE FORMULA
 2. Metal complex according to claim 1, wherein M denotes a nickel, copper or cobalt atom.
 3. The compound of the formula
 4. The compound of the formula
 5. The compound of the formula
 6. The 1:2-cobalt-complex of the dyestuff of the formula
 7. The 1:2-cobalt-complex of the dyest. of the formula 